Acyl quinone sulphonamides as printing aids



Patented Au'g. 21, 1945 ACYL QUINONE sunrnommpas as rnm'rmo ams Roy H.Kienle and Chester A. Amick, Bound I Brook, N. J.', asslgnors toAmerican Cyanamid Company, New Yorlr, N. E, a corporation or Maine NoDrawing. Application .lluly 1, 1943,

Serial No. 493,132

10 Claims. (Gil. 8-70) This invention relates to a. new type of dyeingand printing assistant, dye compositions containing these assistants andproducts printed there- I from.

Use of printing-color pastes containing dyes, particularly in printingoperations using vat dyes, is sufliciently well-known so that theprocedure has become almost standardized. The actual color source may beeither a dye paste or a dye powder. In addition to the real color, a dyepaste usually contains agents to prevent dryingout, settling and/orfreezing. Dye powders, not being subject to these difficulties, do notrequire these agents but they usually contain agents or areso processedas to promote dispersibility.

In either case, the dye powder must be admixed with suitable thickener,usually a gum dispersion, to form a printing-color paste which issuitable for application. Inthe case of vat dyes, it is also necessarytoadd a reducing agent and usually an alkali. Because the color yield fromprinting-color pastes often decreases rapidly as the paste ages afterbeing made up, theseprlnting-color pastes are usually prepared bythefabric finishers just before they are to be used.

The printing-color pastes, however compounded, are then applied totextile, paper or other fabric materials for decorative or protectivepurposes. The printed pieces are dried, aged in a steam ager, treatedwith an oxidizing agent, rinsed and finally dried. Usually in processingtextiles, the printed fabric also is so'aped at or near the boil withabout a 0.1% soap solution and again rinsed before the final dryingoperation.

In making up and applying printing-color pastes it has been found that amaterial suit-- able for use as a printing assistant is of advantage inobtaining maximum color yield. The exact way in which these materialsact to produce an improved color yield in printing is not entirelyunderstood. It is with these printing aids -or assistants that thepresent invention is parall facture of the paste is" not only easier,but in addition they are thus generally more uniformly dispersedthroughout a printing-color paste made therefrom. As a result, theprinting assistants usually operate more -eiiiectively when theprinting-color paste is finally applied to thefabric.

His only relatively recently that dye powders suitable for use in makingup printing-color pastes have been available. Most of the printing aidspreviously used in dye pastes, being either liquid in form or extremelyhydroscopic, can not be used with dye powders, the latter beingnecessarily limited to the use of dry solids. Nevertheless, it isdesirable that printing assistants be incorporated in the powders at thetime of manuporated in a dye powder, a solid printing aid is necessary.Examples of such solids which have been used in the past include thehydrochlorides were intended. Others, such as the polyhydric alcohols,cause deterioration of the printing-color pastes so that markedvariations in the strength of prints therefrom are observable even afterthe printing-color paste has been allowed to stand for only a relativelyshort time. Many of them are satisfactory with some colors but have anadverse effect onothers, even to the extent of visibly altering theshade. None of them are suitable without modification for use both inpaste and powder compositions. 7

There remains, therefore, a demand for suitable printing assistantswhich will produce a satisfactory color intensification and will notcause fore, Qhiqqt of the present invention to proto yield good results.

vide a new type of printing assistant which posv sesses these desirableproperties.

In general the objects of the present invention are accomplished byusing as a printing assistant a substituted quinone-sulphonamide havinga terminal acyl group. These compounds may be represented by the generalformula in which Q represents the residue of a qulnone such as alphaorbeta-anthraquinone and betanaphthoquinone; R represents the residue of acarboxylic acid amide and z may be one or two. Typical of thesulphonamides of the present invention is the condensation product ofbeta-anthraquinone-sulphonic acid and acetamide which has the probableformula So far as the present invention is concerned the assistants maybe added to the printing-color pastes at any point. They may beincorporated into the thickener; into the dye pastes or powders or maybe blended directly into the printing-color paste. However, as pointedout above, it is preferable that they be incorporated in the dye pasteor powder during manufacture.

In preparing the quinone-sulphonamide derivatives used as printingassistants according to the present invention, the qulnonyl residueexample as beta-anthraquinone sulphonyl chloride, with an acid amide,such as acetamide. This exemplary reaction will give an excellent printing assistant having the formula set forth above.

The invention however is not so limited. Sui-table printing assistantsmay be prepared by condensing the quinone-sul'phonic acid withsubstantially any cyclic or aliphatic acid monoamide.

Of the cyclic acid amides which can be used to form excellent printingassistants according to the present invention phthalimide is perhaps themost commonly available and since it works well is perhaps preferable.Others however may be used. The aliphatic acid amides may be eithermonoor dibaslc and may be either saturated or unsaturated. Preferablythese acids are chosen from the'group having from about 2 to 8 carbonatoms since the amide of larger acids tend to cause polymerization. ofthe monobasic acid amides, acetamlde as noted above is typical. Amidesof propionic, butyric acid and the like also give excellent printingassistants. Unsaturated aliphatic acid monoamides of fumaric, maleic',itaconic and the like acids also were found Similarly such. saturatedaliphatica'cids as oxalic, succinic, glutaric, adipic,

sebacic, and the like, for example, were found to be suitable. 7

While the dye and printing paste compositions of the present inventionare not limited to the use of any particular'dyes or dye forms, they areespecially suitable for use with vat-dyes in either paste or powderform. Particularly good results may be obtained using the vat-dyepowders of high autodispersibility set forth in Crossley et al., UnitedStates Reissue Patent 21,402, reissued March 19, 1940. By combining thecolor materials of that patent into printing-paste compositionscontaining the printing assistants of the present invention, the full'advantages of both may be gained with a resultant simplicity in use andexcellence of shade and sharpness of color.

The invention will be more fully. set forth in connection with thefollowing examples which are intended to be illustrative and not by wayof limitation. All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on two diiferentfabrics. When rayon is referred to,.a titanium-dioxide pigmented, allviscose-rayon flat crepe was used. The cotton fabric referred to is an x80 bleached, unmercerized, cotton print-cloth. Agelngof the prints wascarried out in a steam ager which was constructed in such a manner thatcontrolled temperatures could be used. The temperature range normallyused was -105 0. Those ageings referred to as plant or hot ageings werecarried out in the temperature range of about 106--110 C. In the case ofthe cotton prints ageing periods of 3 minutes,- 5 minutes or both wereused. On rayon, ageing periods of 5 and' 10 minutes or both were used.The shortest period which gives a satisfactory ageing is preferable.

of water and the mixture was heated with continuous stirring until thetemperature reached also " about 185 F. Heating was continued for about1 hours after .which 450 parts of powdered potassium carbonate and 450parts of powdered sodium carbonate were added and the mixture stirreduntil the carbonates dissolved. Heating was discontinued but stirringwas continued until the temperature reached approximately 150 F. atwhich time 700 parts of sodium sulphoxylate were dissolved therein, 600parts of glycerine were added and the paste bulked to 10,000 parts.Stirring was continued until the paste cooled to room temperature. Inthe succeeding examples this paste is referred to as thickener A.

Example 2 2,100 parts of 3-2 British gum, 200 parts of tapioca flour and500 parts of cornstarch were added to 2,500 parts of water and heatedover a steam bath for approximately 1 hours with continuous stirringuntil the temperature reached about 185 F. The source of heat was thenremoved but stirring was continued until the temperature decreased to F.at which time 3,100 parts of potassium carbonate which had beenpreviously dissolved in hot water was added to the cooked gum. 1,100parts of sodium sulphoxylate formaldehyde were added to the commonmixture at a temperature of about F. Subsequently, 1,400 parts ofglycerine were added and after thorough stirring'the whole was bulked toabout 10,000 parts. This mixture was cooled and stirred continuouslyuntil the mass reached room temperature. m the succeeding examples thismixture is referred to as thickener B.

Example 3 1,500 parts oi. water at a temperature ci' about 140 F. andadded to the common mixture with stirring until the whole was thoroughlymixed. 360 parts of glycerine were added and alter thorough stirring thewhole was bulked to about 12,000 parts. In the succeeding examples thisis referred to as thickener C.

Example 4 2.5 parts of a Dark Blue BO dispersed powder (0. I.-1099),prepared according to U. S. Reissue Patent 21,402 and containing about0.9 part oi real color, were blended with 0.25 part of the condensationproduct of beta-anthraquinonesulphonic acid with acetamide. This mixturewas made into a paste with 97.25 parts of thickener A. A second 5 partsof Dark Blue BO dispersed powder was made into a paste in the samemanner except that no printing assistant was added. Each of these pasteswere printed on rayon and cotton. The printed pieces were air dried,aged in a steam ager, oxidized, rinsed, soaped at the boil in an 0.1%soap solution for 5 minutes, rinsed again and ironed dry. Prints fromthe paste containing the printing assistant were much stronger andbrighter.

Example 5 Example 4 was duplicated except that the reaction productobtained from alDha-anthraquinone-sulphonic 'acid' and acetamide wasused in place or the printing assistant of the preceding example. Againthe prints obtained from the paste containing the printing assistant wasstronger and brighter than those obtained from the paste containingcolor only.

Example 6 Example 4 was duplicated except that 2.5 parts of GoldenOrange G powder (C. I.--1096) containing about 0.5 part of real colorwas substituted from the Dark Blue B0 of Example 4. Prints obtained fromthe paste containing the printing assistant were definitely stronger,

brighter and more even than those obtained from r the paste in which noprinting assistant was present.

Example 7 Example 6 was duplicated'using the printing assistant ofExample 5. Satisfactory results essentially the same as those 01 Example6 were obtained.

Example 8 A sample of wet presscake of Vat Orange R- (C. I.-121'l) wasdispersed with a sodium salt of disulpho-dinaphthylme'thane and adjustedwith water to contain 12% of real dye. Ten parts of this mixture weremixed with 0.5 part of the condensation product ofanthraquinone-beta-sulphonic acid and maleyl-amlde. In this "casethickener C was used. Each of these pastes were printed on rayon andcotton.- The results obtained from the paste containing the printingassistant were much stronger and brighter than those obtained from thepaste in which no printing assistant was present.

Example 9 The procedure of Example '8 was duplicated except that thereaction product of alpha-anthraquinone-sulphonic acid and maleyl amidewas used in place of the printing assistant described in Example 8. Eachof the pastes were printed on samples of rayon and cotton. Test printsobtained from the paste in which the printing assistant was used werestronger and brighter than those obtained in' which no printingassistant was present.

Example 10 The procedure of Example 8 was duplicated except that thecondensation product of betaanthraquinone-sulphonic acid with succinylamide was used. Prints obtained from the paste-in which the printingassistant was present again proved to be stronger and brighter thanthose obtained from the paste in which only printing thickener is used.This was particularly true when aged under commercial ageing conditions.

Example 11 Example 8 was repeated using the condensation product ofbeta-anthraquinone-sulphonic acid and fumaric acid as the printingassistant. This product gave excellent strength and brightness whencompared with prints obtained from pastes in which no printing assistantwas used.

Example 12. The procedure of Exampl 8 was duplicated except that thecondencation product of betaanthraquinone-sulphonic acid and phthalimidewas used as the printing assistant. Again the prints obtained from thepastes in which the assistant was used were much stronger and brighterthan the prints obtained in which no printing assistant was used.

Example 13 Example 4 was duplicated except that Vat Brown RR dispersedpowder containing about 0.8 part of real color was used in the place ofthe Dark Blue 130. Prints obtained from the paste in which the printingassistant was used were very much stronger than the prints obtained fromthe pastes containing no printing assistant. This assistant produced themaximum color value of the'Vat Brown RR in a much shorter ageing timethan was possible and gave better color yields than when no printingassistant was used. This is of definite commercial advantage.

We claim: I a

1. A color composition comprising a vat dye and a quinone-sulphonamidederivative having the general formula onset-me in which Q represents aquinonyl radical selected] from the group consisting ofbeta-naphthoquinonyl and the anthraquinonyl radicals, R represents theresidue of an amide selected from the group consisting of the aliphaticmonocarboxylic acid amides and the monoamides of the aliphaticdicarboxylic acids having from 2 to- 8 carbon atoms, phthalimide, andthe monoamides of cyclic-dicarboxylic acids and :l: is a small wholenumber selected from the group consisting of i and 2.

2. A dye powder composition comprising a vat.

dye and a powdered quinonyl sulphonamide derivative having the generalformula in which Q represents a quinonyl radical selected from the groupconsisting of beta-naphthaquinonyl and the anthraquinonyl radicals, Rrepresents the residue of an amide selected from the group consisting ofthe aliphatic monocarboxylic acid amides and the monoamides of'thealiphatic dicarboxylic acids having from 2 to 8 carbon atoms,phthalimide, and the monoamides of cyclic-dicarboxylic acids and a: is asmall whole number selected from the group consisting of 1 and 2.

3. A dye powder composition comprising a vat dye powder of highautodispersibility, and a powdered quinonyl sulphonamide derivativehaving the general formula in which Q represents a quinonyl radicalselected from the group consisting of beta-naphthoquinonyl and theanthraquinonyl radicals, R represents the residue of an amide selectedfrom the group consisting of the aliphatic monocarboxylic acid amidesand the monoamides oi the aliphatic dicarboxylic acids having from 2 to8 carbon atoms, phthalirnide, and the monoamides of .cyclic-dicarboxylicacids and a: is a small whole number selected from the group consistingof 1 and 2.

4. A color composition according to claim 1 in which Q represents thebeta-naphthoquinonyl group. a

5. A color composition according to claim 1 in which Q represents ananthraquinonyl group.

6. A printing paste composition comprising a vat dye, a thickener, and aquinone-sulphonamide derivative having the general formula Q(SO:R)= inwhich Q represents a quinonyl radical selected from the group consistingof beta-naphthoquinonyl and anthraquinonyl radicals, R represents theresidue'of an amide selected from the group consisting of the aliphaticmonocarboxylic acid amides and the monoamides of the aliphaticdicarboxylic acids having from 2 to 8 carbon atoms, r

phthalimide, and the monoamides of cyclic-dicarboxylic acids and a: is asmall whole number selected from the group consisting of l and 2.

8. A printing paste composition comprising a highly-dispersed vat dye,a, thickener and a quinone-sulphonamide derivative having the generalformula phthalimide, and the monoamides'oi cyclicdicarboxylic acids anda: is a small whole number selected from the group consisting of 1 and 2obtainable by compounding a colloidized vat dye powder of highautodispersibility and the qui-.

none-sulphonamide derivative with the thickener.

9. A method or printing with vat color which 7 comprises printing afabric with a printing paste composition comprising a vat dye, athickener and a quinone-sulphonamide derivative having the generalformula in which Q represents a quinonyl radical selected from the groupconsisting'of beta-naphthoquinonyl and anthraquinonyl radicals, Rrepresents the residue of an amide selected from the group consistingof'the aliphatic monocarboxylic acid amides and themonoamides of thealiphatic-dicarboxylic acids having from 2 to 8 carbon atoms,phthalimide, and the monoamides of cyclic-dicarboxylic acids and a: is asmall whole number selected from the group consisting oi land 2.

10. An article oi manufacture comprising a fabric printed with acomposition comprising a vat dye and a quinone-sulphonamide derivativehavingthe general formula selected from the group consisting of 1 and 2.

ROY H. KIENLE. CHESTER A. ANIICK.

CERTIFICATE 0F CORRECTION. Patent No. 2585,5955 August 21, 191

ROY H. KIENLE, ET ALQ;

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as folluws: Page 14.,first column, line 50, claim 6, after onyl I insert -andanthraquinonyl-; line 58, claim 7, for the word "vast" read -vat-- andthat the said Letters Patent should be read with this correction thereinthat the sameomay conform to the, record of the case in the PatentOfficew Signed and sealed this 12th day of February, A. DB 191;

. 1 Leslie Frazer Y (Seal) First Assistant Commissioner of Patents 5

